CH635108A5 - METHOD FOR PRODUCING REACTION MIXTURES THAT ARE SUITABLE AS INITIATORS FOR RADICALLY INITIATABLE POLYMERIZATION REACTIONS. - Google Patents
METHOD FOR PRODUCING REACTION MIXTURES THAT ARE SUITABLE AS INITIATORS FOR RADICALLY INITIATABLE POLYMERIZATION REACTIONS. Download PDFInfo
- Publication number
- CH635108A5 CH635108A5 CH882577A CH882577A CH635108A5 CH 635108 A5 CH635108 A5 CH 635108A5 CH 882577 A CH882577 A CH 882577A CH 882577 A CH882577 A CH 882577A CH 635108 A5 CH635108 A5 CH 635108A5
- Authority
- CH
- Switzerland
- Prior art keywords
- atoms
- initiators
- mol
- acid
- alkyl
- Prior art date
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- 239000003999 initiator Substances 0.000 title claims description 44
- 239000011541 reaction mixture Substances 0.000 title claims description 19
- 238000006116 polymerization reaction Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 aryl ketone Chemical class 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- UCFFGYASXIPWPD-UHFFFAOYSA-N methyl hypochlorite Chemical compound COCl UCFFGYASXIPWPD-UHFFFAOYSA-N 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910003910 SiCl4 Inorganic materials 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 26
- 229910052749 magnesium Inorganic materials 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical class C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 14
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 10
- 239000012965 benzophenone Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920006305 unsaturated polyester Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 2
- DFYJCXSOGSYMAJ-UHFFFAOYSA-N (4-tert-butylphenyl)-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 DFYJCXSOGSYMAJ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- VMFJVWPCRCAWBS-UHFFFAOYSA-N (3-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 VMFJVWPCRCAWBS-UHFFFAOYSA-N 0.000 description 1
- AOJURBVPQULQLT-UHFFFAOYSA-N (4,4-dimethylcyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(C)(C)CC=C1C(=O)C1=CC=CC=C1 AOJURBVPQULQLT-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- YVPZFPKENDZQEJ-UHFFFAOYSA-N 4-propylcyclohexan-1-ol Chemical compound CCCC1CCC(O)CC1 YVPZFPKENDZQEJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001006 Constantan Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 108010076830 Thionins Proteins 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KUXMPPPSUQZGRR-UHFFFAOYSA-N bis(2-ethenylphenyl) carbonate Chemical class C=CC1=CC=CC=C1OC(=O)OC1=CC=CC=C1C=C KUXMPPPSUQZGRR-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- AXTPGQHJFRSSQJ-UHFFFAOYSA-N dichloro-ethoxy-methylsilane Chemical compound CCO[Si](C)(Cl)Cl AXTPGQHJFRSSQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- QPOIJJUKCPCQIV-UHFFFAOYSA-N diphenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 QPOIJJUKCPCQIV-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003828 free initiator Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- IQCYANORSDPPDT-UHFFFAOYSA-N methyl(silyl)silane Chemical compound C[SiH2][SiH3] IQCYANORSDPPDT-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000000214 vapour pressure osmometry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0442—Catalysts
- C08F299/0471—Other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
- Polymerization Catalysts (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Aufgabe der vorliegenden Erfindung war es, Substanzen bereitzustellen, die sich als Initiatoren für radikalische Polymerisationsreaktionen eignen, wobei ihre initiierende Wirkung aber nicht auf den Reaktionsmöglichkeiten der Peroxidgruppierung basieren sollte. Die gewünschten Substanzen sollten ferner bei Zimmertemperatur in den polymerisierbaren Systemen gut lagerstabil sein, bei höheren Temperaturen aber die bereits be-5 kannten peroxidfreien Initiatoren hinsichtlich ihrer Reaktivität bei möglichst geringen Konzentrationen im polymerisationsfähigen System noch übertreffen. The object of the present invention was to provide substances which are suitable as initiators for radical polymerization reactions, but their initiating action should not be based on the reaction options of the peroxide grouping. The desired substances should also have good storage stability at room temperature in the polymerizable systems, but at higher temperatures they should still exceed the known peroxide-free initiators in terms of their reactivity at the lowest possible concentrations in the polymerizable system.
Überraschenderweise wurde nun gefunden, dass die Umsetzung von unedlen Metallen, vorzugsweise von Metallen der 1. io und 2. Hauptgruppe des Periodensystems, insbesondere von Lithium, Natrium, Kalium, Magnesium oder Calcium, sowie Aluminium mit den im Anspruch 1 definierten a-Arylketonen oder Arylaldehyden und chlorierten Silicum-Verbindungen in den dort angegebenen Mengenverhältnissen, in einem inerten 15 aprotischen Lösungsmittel leicht und in sehr hoher Ausbeute zu Reaktionsgemischen führen, die bereits in geringen Konzentrationen teilweise schon bei einer Temperatur ab 40 °C eine schnelle und vollständige Durchhärtung der zu polymerisieren-den Substanzen bewirken. Ausserdem zeichnen sich polymeri-20 sationsfähige Systeme mit einem Gehalt an derartigen initiierenden Reaktionsgemischen durch eine relativ hohe Lagerstabilität aus. Ein weiterer Vorteil solcher Initiatoren ist es, dass sie beim Zerfall in Radikale keine flüchtigen Substanzen freisetzen, die im Polymerisat eine unerwünschte Blasenbildung hervorru-25 fen können. Surprisingly, it has now been found that the reaction of base metals, preferably metals of the 1st and 2nd main groups of the periodic table, in particular lithium, sodium, potassium, magnesium or calcium, and aluminum with the a-aryl ketones or Aryl aldehydes and chlorinated silicon compounds in the proportions given therein, in an inert 15 aprotic solvent, easily and in very high yield lead to reaction mixtures which, even in low concentrations, polymerize quickly and completely at temperatures as low as 40 ° C. - cause the substances. In addition, polymerizable systems with a content of such initiating reaction mixtures are distinguished by a relatively high storage stability. Another advantage of such initiators is that when they break down into radicals, they do not release any volatile substances that can cause undesired blistering in the polymer.
Gegenstand der Erfindung ist das im Patentanspruch 1 definierte Verfahren zur Herstellung derartiger Reaktionsgemische. The subject matter of the invention is the method for producing such reaction mixtures as defined in claim 1.
Im erfindungsgemässen Verfahren wird als unedles Metall vorzugsweise ca. 0,5 mol eines Metalls der 2. Hauptgruppe des 30 Periodensystems, wie Magnesium oder Calsium, oder ca. 1 mol eines Metalls der 1. Hauptgruppe des Periodensystems, wie Lithium, Natrium oder Kalium oder ca. 'A mol eines Metalls der 3. Hauptgruppe des Periodensystems, wie Aluminium, eingesetzt, und die Umsetzung im inerten aprotischen Lösungsmittel 35 wird vorzugsweise bei — 5 bis +50 °C - sofern notwendig unter Kühlung—vorzugsweise mit 0,5 bis 0,6 mol des Dichlororgano-silans der Formel VII oder mit vorzugsweise 0,3 bis 0,4 mol des Trichlororganosilans der Formel VIII oder mit 0,1 bis 0,7 mol eines Polyorganosilans oder -siloxans, das vorzugsweise 2 bis 6 40 an Si gebundene Chloratome enthält und ein Molekulargewicht von 150 bis 1500 ausgeführt. In the process according to the invention, the base metal is preferably about 0.5 mol of a metal of the 2nd main group of the periodic table, such as magnesium or calcium, or about 1 mol of a metal of the 1st main group of the periodic table, such as lithium, sodium or potassium or approx. 'A mol of a metal of the 3rd main group of the periodic table, such as aluminum, and the reaction in the inert aprotic solvent 35 is preferably at -5 to +50 ° C - if necessary with cooling - preferably with 0.5 to 0 , 6 mol of the dichloro-organosilane of the formula VII or preferably 0.3 to 0.4 mol of the trichloro-organosilane of the formula VIII or with 0.1 to 0.7 mol of a polyorganosilane or -siloxane which preferably contains 2 to 6 40 of Si contains bound chlorine atoms and has a molecular weight of 150 to 1500.
Ein weiterer Gegenstand der Erfindung sind die nach dem erfindungsgemässen Verfahren hergestellten Reaktionsgemische. The invention further relates to the reaction mixtures prepared by the process according to the invention.
45 Die erfindungsgemäss einzusetzenden Chloratom-haltigen Polyorganosilane und Polyorganosiloxane können 2 bis 20 Sili-ciumatome enthalten; die nicht durch Silicium, Chlor und Siloxy abgesättigten Valenzen tragen z.B. aliphatische, cyclo-aliphati-sche oder aromatische Gruppen mit 1-20, vorzugsweise 1-6 50 Kohlenstoffatomen, insbesondere Methyl, Äthyl, Phenyl. 45 The chlorine atom-containing polyorganosilanes and polyorganosiloxanes to be used according to the invention can contain 2 to 20 silicon atoms; which carry valences not saturated by silicon, chlorine and siloxy e.g. aliphatic, cycloaliphatic or aromatic groups with 1-20, preferably 1-6 50 carbon atoms, especially methyl, ethyl, phenyl.
Die Molekulargewichte einzelner Fraktionen der erfindungsgemäss hergestellten Reaktionsgemische Lassen sich gel-chromatographisch (mittels Eichsubstanzen) bestimmen. The molecular weights of individual fractions of the reaction mixtures produced according to the invention can be determined by gel chromatography (using calibration substances).
Als Beispiele für die als Ausgangsmaterialien einzusetzen-55 den Aldehyde bzw. ICetone und Silane werden im folgenden verschiedene Reaktionspartner ausgeführt: Various reaction partners are listed below as examples of the aldehydes or ICetones and silanes to be used as starting materials:
1) Magnesium 1) Magnesium
2) Magnesium 2) Magnesium
3) Magnesium 3) magnesium
4) Magnesium 4) Magnesium
5) Natrium 5) sodium
6) Magnesium 6) Magnesium
7) Lithium 7) Lithium
8) Magnesium 8) Magnesium
9) Magnesium 9) Magnesium
10) Magnesium 10) Magnesium
11) Natrium 11) sodium
Benzaldehyd Benzaldehyde
Benzaldehyd Benzaldehyde
Benzaldehyd Benzaldehyde
Acetophenon Acetophenone
Acetophenon Acetophenone
Propiophenon Propiophenon
Isopropylphenylketon Isopropylphenyl ketone
Cyclohexylphenylketon Cyclohexylphenyl ketone
Benzophenon Benzophenone
Benzophenon Benzophenone
Benzophenon Benzophenone
Trichlormethylsilan Trichloromethylsilane
Trichlorphenylsi lan Trichlorophenylsil
Dichlordimethylsilan Dichlorodimethylsilane
Trichlormethylsilan Trichloromethylsilane
Diphenyldichlorsilan Diphenyldichlorosilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Dichlordimethylsilan Dichlorodimethylsilane
Trichlorphenylsilan Trichlorophenylsilane
3 3rd
635 108 635 108
12) Lithium 12) Lithium
13) Kalium 13) potassium
14) Calcium 14) Calcium
15) Magnesium 15) Magnesium
16) Natrium 16) sodium
17) Magnesium 17) Magnesium
18) Magnesium 18) Magnesium
19) Magnesium 19) Magnesium
20) Magnesium 20) Magnesium
21) Magnesium 21) Magnesium
22) Magnesium 22) Magnesium
23) Magnesium 23) Magnesium
24) Aluminium 24) aluminum
25) Magnesium 25) Magnesium
26) Aluminium 26) aluminum
27) Magnesium 27) Magnesium
28) Magnesium 28) Magnesium
29) Aluminium 29) aluminum
4,4-Dimethylbenzophenon 4,4-dimethylbenzophenone
Benzophenon Benzophenone
4-t-Butylbenzophenon 4-t-butylbenzophenone
4-Chlorbenzophenon 4-chlorobenzophenone
2-Methylbenzophenon 2-methylbenzophenone
2-Chlorbenzophenon 2,4-Dichlorbenzophenon 2-chlorobenzophenone 2,4-dichlorobenzophenone
3-Methoxybenzophenon Naphthylphenylketon 3-methoxybenzophenone naphthylphenyl ketone
4-Phenylbenzophenon 4-Benzoylbenzophenon Benzaldehyd Acetophenon 4-phenylbenzophenone 4-benzoylbenzophenone benzaldehyde acetophenone
Acetophenon Acetophenone
Isopropylphenylketon Isopropylphenyl ketone
Benzophenon Benzophenon Benzophenone Benzophenone
Benzophenon Benzophenone
30) Natrium 30) sodium
2-Chlorbenzophenon 2-chlorobenzophenone
Trichlormethylsilan Trichloromethylsilane
Dichlordiphenylsilan Dichlorodiphenylsilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Dichlordimethylsilan Dichlorodimethylsilane
Trichlormethylsilan Trichloromethylsilane
Trichloräthylsilan Trichloroethylsilane
Dichloräthoxymethylsilan Dichloroethoxymethylsilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Trichlormethylsilan Trichloromethylsilane
Tetrachlorsilan Carbon tetrachloride
1,2-Dichlortetra- 1,2-dichlorotetra-
methyldisilan methyldisilane
Tetrachlorsilan Carbon tetrachloride
CH3 / CH3\ CH3 ! / i \ ! Cl-Si- O-Si I-O-Si-Cl CH3 / CH3 \ CH3! / i \! Cl-Si-O-Si I-O-Si-Cl
I l I / I ch3\ ch3/2 ch3 I l I / I ch3 \ ch3 / 2 ch3
Tetrachlorsilan 1,1,2-Trichlortrimethyldisilan Tetrachlorosilane 1,1,2-trichlorotrimethyldisilane
/ CH3 CH3 / CH3 CH3
/ ' ' / ''
CH3-Si l-O-S i-O-S i-Cl CH3-Si l-O-S i-O-S i-Cl
\ CH3 CH3 /3 \ CH3 CH3 / 3
ch3 / ch3\ ch3 I / I \ [ Cl-Si-Io-Si I-O-Si-Cl I \ I J I ch3\ ch3/56 ch3 ch3 / ch3 \ ch3 I / I \ [Cl-Si-Io-Si I-O-Si-Cl I \ I J I ch3 \ ch3 / 56 ch3
31) Magnesium 31) Magnesium
3-Methoxybenzophenon 3-methoxybenzophenone
1,2,3,4-Tetrachlorhexa-methylentetrasilan 1,2,3,4-tetrachlorohexa-methylenetetrasilane
32) Lithium 32) Lithium
4-tert.-Butylbenzophenon ch3 ch3 4-tert-butylbenzophenone ch3 ch3
Si| O-S i-O-S i-Cl CH3 CH3 / 4 Si | O-S i-O-S i-Cl CH3 CH3 / 4
Inerte aprotische Lösungsmittel sind z.B. Aromaten und Al-kylaromaten, wie Benzol und Toluol; Äther, wie Diäthyläther, Diisopropyläther, Dibutyläther, Anisol, Tetrahydrofuran, Di-oxan, 1.2-Dimethoxyäthan; Trialkylphosphate, wie Triäthyl-phosphat, Tributylphosphat; N.N-disubstituierte Amide, wie Dimethylformamid, N.N-Dimethylacetamid und Phosphorsäu-retris-(dimethylamid). Weitere geeignete Lösungsmittel sind in Methoden der Organischen Chemie (Houben-Weyl), Bd. XIII/ 2 a, S. 59-70, Georg Thieme-Verlag, Stuttgart 1973, beschrieben. Als besonders geeignet erwiesen sich Lösungsmittelgemische von 0-80 Gew.-Teilen Benzol oder Toluol, 2-98 Gew.-Teilen Tetrahydrofuran und 2-98 Gew.-Teilen Triäthilphos-phat oder Phosphorsäuretris-(dimethylamid). Um das Reaktionsgemisch nicht unnötig zu verdünnen, wird im allgemeinen möglichst wenig Lösungsmittel eingesetzt. In der Regel ist ein Ketoverbindung/Lösungsmittel-Gewichtsverhältnis von 1:1 vollkommen ausreichend. Inert aprotic solvents are e.g. Aromatics and alkyl aromatics such as benzene and toluene; Ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, di-oxane, 1,2-dimethoxyethane; Trialkyl phosphates, such as triethyl phosphate, tributyl phosphate; N.N-disubstituted amides such as dimethylformamide, N.N-dimethylacetamide and phosphoric acid retris (dimethylamide). Other suitable solvents are described in Methods of Organic Chemistry (Houben-Weyl), Vol. XIII / 2a, pp. 59-70, Georg Thieme-Verlag, Stuttgart 1973. Solvent mixtures of 0-80 parts by weight of benzene or toluene, 2-98 parts by weight of tetrahydrofuran and 2-98 parts by weight of triethophosphate or phosphoric acid tris (dimethylamide) have proven particularly suitable. In order not to dilute the reaction mixture unnecessarily, as little solvent as possible is generally used. As a rule, a keto compound / solvent weight ratio of 1: 1 is completely sufficient.
Es empfiehlt sich zu berücksichtigen, dass unter den Reaktionsbedingungen schon teilweise Zersetzung möglich ist. Falls also das erfindungsgemäss hergestellte Reaktionsgemisch geringe Reaktivität aufweisen soll, die auf eine Zersetzung der als 50 Initiator wirksamen Verbindungen während der Herstellung zurückzuführen ist, empfiehlt sich eine Herabsetzung der Reaktionstemperatur. It is advisable to take into account that partial decomposition is already possible under the reaction conditions. If the reaction mixture prepared according to the invention is to have low reactivity, which can be attributed to the decomposition of the compounds which act as initiators during production, it is advisable to lower the reaction temperature.
Die erfindungsgemäss hergestellten Reaktionsgemische zeichnen sich durch hohe Reaktivität aus. So übertreffen sie die 55 monomeren Benzpinakolderivate hinsichtlich ihrer Reaktivität beträchtlich. The reaction mixtures produced according to the invention are notable for high reactivity. In this way, they significantly outperform the 55 monomeric benzpinacol derivatives in terms of their reactivity.
Die erfindungsgemäss hergestellten Reaktionsgemische sind teilweise bereits bei einer Temperatur oberhalb 40 °C wirksam. Eine vollständige und rasche Durchhärtung wird in der Regel 60 bei Einsatz von 0,02 bis 1, vorzugsweise 0,05 bis 0,8, Gew.-%, Reaktionsmischung, bezogen auf die zu polymerisierende Substanz, erreicht. Some of the reaction mixtures prepared according to the invention are effective even at a temperature above 40 ° C. Complete and rapid curing is generally achieved using 0.02 to 1, preferably 0.05 to 0.8,% by weight of reaction mixture, based on the substance to be polymerized.
Der Beginn der Polymerisationsreaktion wird durch Erhitzen einer Mischung aus zu polymerisierender Substanz und Re-65 aktionsmischung über eine konkrete, im Einzelfall leicht zu bestimmende Anspringtemperatur, erreicht. Die Härtung radikalisch polymerisierbarer Systeme erfolgt in der Regel zwischen 60 und 200 °C. The start of the polymerization reaction is achieved by heating a mixture of the substance to be polymerized and the reaction mixture above a specific light-off temperature which is easy to determine in individual cases. Systems which can be polymerized by free radicals are generally cured between 60 and 200 ° C.
635 108 635 108
Die Härtung kann in einem Zuge, falls erwünscht aber auch stufenweise, erfolgen (vgl. GB-PS-1 041 641). The hardening can be carried out in one go, but also stepwise if desired (cf. GB-PS-1 041 641).
Es ist möglich, durch eine einfache Farbreaktion die Anspringtemperatur der erfindungsgemäss hergestellten Initiatorreaktionsmischungen festzustellen: Die bei der thermischen Zersetzung entstehenden Radikale können nämlich chinoide Farbstoffe entfärben. Zur Durchführung des Tests löst man eine geringe Menge chinoiden Farbstoffs, z.B. Methylenblau, Thio-nin oder Neutralrot, in einem Lösungsmittel, das frei von molekularem Sauerstoff ist, z.B. Glykol, Xylol, und setzt eine mindestens äquivalente Menge der Reaktionsmischung zu. Die Temperatur, bei der der Farbstoff entfärbt wird, ist die Anspringtemperatur der Initiator-Reaktionsmischung. It is possible to determine the light-off temperature of the initiator reaction mixtures prepared according to the invention by means of a simple color reaction: the radicals formed during thermal decomposition can decolorize quinoid dyes. A small amount of quinoid dye, e.g. Methylene blue, thio-nin or neutral red, in a solvent that is free of molecular oxygen, e.g. Glycol, xylene, and add an at least equivalent amount of the reaction mixture. The temperature at which the dye is decolorized is the light-off temperature of the initiator reaction mixture.
Die Anspringtemperatur hängt stark von der Struktur der Verbindungen ab. Initiatoren mit vielen raumfüllenden (z.B. Aryl-)Resten zeichnen sich (insbesondere bei orthosubstitu-ierten Arylresten) durch eine relativ niedrige Anspringtemperatur aus. Andere Initiatoren zerfallen erst bei höheren Temperaturen und sind unter Umständen in der zu polymerisierenden Substanz bis zu 80 °C noch stabil. The light-off temperature strongly depends on the structure of the compounds. Initiators with many space-filling (e.g. aryl) residues are characterized (especially in the case of ortho-substituted aryl residues) by a relatively low light-off temperature. Other initiators only disintegrate at higher temperatures and may still be stable up to 80 ° C in the substance to be polymerized.
Als Substanzen, deren Polymerisation durch-die erfindungsgemäss hergestellten Reaktionsgemische initiiert werden kann, kommen alle radikalisch polymerisierbaren Verbindungen oder Gemische in Betracht, z.B. also konjugierte Diene, wie Butadien, Isopren, Chloropren; Vinylchlorid, Vinylidenchlorid ; aromatische Vinylverbindungen, wie Styrol, Divinylbenzol; Vinyl-ester, insbesondere Vinylacetat und Vinylpropionat; Vinyl-äther, wie Vinylpropyläther, Vinylisobutyläther; Acrylsäure und Methacrylsäure und deren Derivate, wie Ester, insbesondere mit aliphatischen Alkoholen mit 1 bis 5 C-Atomen, Nitrile, Amide usw. ; Di(vinylphenyl)carbonate; Diallylphthalat, Dial-lylcarbonat, Diallylfumarat; Di(allylphenyl)-carbonate; Polyol-poly(meth)acrylate;N.N'-Methylenbis(meth)acrylamid. Suitable substances whose polymerization can be initiated by the reaction mixtures prepared according to the invention are all compounds or mixtures which can be polymerized by free radicals, e.g. thus conjugated dienes, such as butadiene, isoprene, chloroprene; Vinyl chloride, vinylidene chloride; aromatic vinyl compounds such as styrene, divinylbenzene; Vinyl esters, especially vinyl acetate and vinyl propionate; Vinyl ethers, such as vinyl propyl ether, vinyl isobutyl ether; Acrylic acid and methacrylic acid and their derivatives, such as esters, especially with aliphatic alcohols with 1 to 5 carbon atoms, nitriles, amides, etc.; Di (vinylphenyl) carbonates; Diallyl phthalate, dialyl carbonate, diallyl fumarate; Di (allylphenyl) carbonates; Polyol-poly (meth) acrylates; N.N'-methylenebis (meth) acrylamide.
Besonders geeignete Substanzen für die Polymerisationsin-itiierungmit den erfindungsgemäss hergestellten Reaktionsgemischen sind ungesättigte Polyesterharze, d.h. die Lösungen a, ß-äthylenisch ungesättigter Polyester in damit copolymerisier-baren Monomeren. Particularly suitable substances for the polymerization initiation with the reaction mixtures produced according to the invention are unsaturated polyester resins, i.e. the solutions a, β-ethylenically unsaturated polyester in monomers copolymerizable therewith.
Geeignete a, ß-äthylenisch ungesättigte Polyester sind die üblichen Polykondensationsprodukte mindestens einer a,ß-äthylenisch ungesättigten Dicarbonsäure mit in der Regel 4 oder 5 C-Atomen oder deren esterbildenden Derivate, z.B. ihren Anhydriden, ggf. in Abmischung mit bis zu 200 mol-%, bezogen auf die ungesättigten Säurekomponenten, mindestens einer aliphatischen gesättigten mit 4—10 C-Atomen oder einer cycloali-phatischen Dicarbonsäure mit 8-10 C-Atomen oder deren esterbildenden Derivate mit mindestens einer Polyhydroxyver-bindung, insbesondere Dihydroxyverbindung, mit 2-8 C-Ato-men - also Polyester, wie sie bei J. Björksten et al., «Polyesters and their Applications», Reinhold Publishing Corp., New York 1956, beschrieben sind. Suitable α, β-ethylenically unsaturated polyesters are the usual polycondensation products of at least one α, β-ethylenically unsaturated dicarboxylic acid with generally 4 or 5 C atoms or their ester-forming derivatives, e.g. their anhydrides, possibly in a mixture with up to 200 mol%, based on the unsaturated acid components, with at least one aliphatic saturated with 4-10 C atoms or a cycloaliphatic dicarboxylic acid with 8-10 C atoms or their ester-forming derivatives at least one polyhydroxy compound, in particular dihydroxy compound, with 2-8 carbon atoms - i.e. polyester, as described in J. Björksten et al., "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956 .
Beispiele für bevorzugt zu verwendende ungesättigte Dicar-bonsäuren oder ihre Derivate sind Maleinsäure oder Maleinsäureanhydrid und Fumarsäure. Verwendet werden können z.B. jedoch auch Mesaconsäure, Citraconsäure, Itaconsäure oder Chlormaleinsäure. Beispiele für die zu verwendenden aliphatischen gesättigten und cyclo-aliphatischen Dicarbonsäuren oder ihre Derivate sind Phthalsäure oder Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure, Hexa- oder Tetrahydro-phthalsäure bzw. deren Anhydride, Endomethylentetrahydro-phthalsäure oder deren Anhydrid, Bernsteinsäure bzw. Bernsteinsäureanhydrid und Bernsteinsäureester und -Chloride, Adipinsäure, Sebacinsäure. Um schwerentflammbare Harze herzustellen, können z.B. Hexachlorendomethylentetrahydrophthal-säure (Hetsäure), Tetrachlorphthalsäure oder Tetrabrom-phthalsäure verwendet werden. Als zweiwertige Alkohole können Äthylenglykol, Propandiol-1,2, Propandiol-1,3, Diäthylen-glykol, Dipropylenglykol, Butandiol-1,3, Butandiol-1,4, Examples of preferred unsaturated dicarboxylic acids or their derivatives to be used are maleic acid or maleic anhydride and fumaric acid. Can be used e.g. however also mesaconic acid, citraconic acid, itaconic acid or chloromaleic acid. Examples to be used aliphatic saturated and cyclo-aliphatic dicarboxylic acids or their derivatives are phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, hexa- or tetrahydro-phthalic acid or anhydrides thereof, Endomethylentetrahydro-phthalic acid or anhydride, succinic acid or succinic anhydride and Bernsteinsäureester and - Chlorides, adipic acid, sebacic acid. To make flame retardant resins, e.g. Hexachlorendomethylene tetrahydrophthalic acid (hetic acid), tetrachlorophthalic acid or tetrabromophthalic acid can be used. As dihydric alcohols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol,
Neopentylglykol, Hexandiol-1,6,2,2-Bis-(4-hydroxycyclohex-yl)-propan, bis-oxalkyliertes Bisphenol A, Perhydrobisphenol und andere eingesetzt werden. Bevorzugt verwendet werden Äthylenglykol, Propandiol-1,2, Diäthylenglykol und s Dipropylenglykol. Neopentyl glycol, hexanediol-1,6,2,2-bis (4-hydroxycyclohex-yl) propane, bis-oxyalkylated bisphenol A, perhydrobisphenol and others can be used. Ethylene glycol, 1,2-propanediol, diethylene glycol and dipropylene glycol are preferably used.
Weitere Modifikationen sind möglich durch Einbau ein-, Further modifications are possible by installing
drei- und vierwertiger Alkohole mit 1-6 C-Atomen, wie Methanol, Äthanol, Butanol, Allylalkohol, Benzylalkohol, Cyclohex-anol undTetrahydrofurfurylalkohol, Trimethylolpropan, Glyce-10 rin und Pentaerythrit sowie von Mono-, Di- und Triallyläthern und Benzyläthern drei- und mehrwertiger Alkohole mit 3-6 C-Atomen gemäss DE-AS-1 024 654, sowie durch Einbau einbasischer Säuren, wie Benzoesäure, oder langkettiger ungesättigter Fettsäuren, wie Ölsäure, Leinölfettsäure und Ricinenfett-15 säure. trihydric and tetravalent alcohols with 1-6 C atoms, such as methanol, ethanol, butanol, allyl alcohol, benzyl alcohol, cyclohexanol and tetrahydrofurfuryl alcohol, trimethylolpropane, glyce-10 rin and pentaerythritol as well as mono-, di- and triallyl ethers and benzyl ethers and polyhydric alcohols with 3-6 C atoms according to DE-AS-1 024 654, and by incorporating monobasic acids, such as benzoic acid, or long-chain unsaturated fatty acids, such as oleic acid, linseed oil fatty acid and ricinene fatty acid-15.
Die Säurezahlen der Polyester liegen gewöhnlich zwischen 1 und 100, vorzugsweise zwischen 20 und 70, die OH-Zahlen zwischen 10 und 150, vorzugsweise zwischen 20 und 100, und die als Zahlenmittel bestimmten Molekulargewichte Mn zwischen 20 500 und 5000, vorzugsweise zwischen ca. 1000 und 3000, (dampfdruckosmometrisch gemessen in Dioxan und Aceton ; bei differierenden Werten wird der niedrigere als der korrekte angesehen). The acid numbers of the polyesters are usually between 1 and 100, preferably between 20 and 70, the OH numbers between 10 and 150, preferably between 20 and 100, and the number average molecular weights Mn between 20 500 and 5000, preferably between about 1000 and 3000, (measured by vapor pressure osmometry in dioxane and acetone; if the values differ, the lower one is considered the correct one).
2S Als mit den ungesättigten Polyestern copolymerisierbare Vinyl- und Vinylidenverbindungen eignen sich in der Polyestertechnologie gebräuchliche ungesättigte Verbindungen, die bevorzugt a-substituierte Vinylgruppen oder ß-substituierte Al-lylgruppen tragen, bevorzugt Styrol; aber auch beispielsweise 30 kernchlorierte und -alkylierte bzw. -alkenylierte Styrole, wobei die Alkylgruppen 1-4 Kohlenstoffatome enthalten, können, z.B. Vinyltoluol, Divinylbenzol, a-Methylstyrol, tert.-Butylsty-rol, Chlorstyrole ; Vinylester von Carbonsäuren mit 2-6 Kohlenstoffatomen, bevorzugt Vinylacetat ; Vinylpyridin, Vi-3S nylnaphthalin, Vinylcyclohexan, Acrylsäure und Methacrylsäure und/oder ihre Ester (vorzugsweise Vinyl-, Allyl- und Methal-lylester) mit 1-4 Kohlenstoffatomen in der Alkoholkomponente, ihre Amide und Nitrile, Maleinsäureanhydrid, -halb- und -diester mit 1-4 Kohlenstoffatomen in der Àlkoholkomponen-40 te, -halb- und -diamide oder cyclische Imide wie N-Methylma-leinimid oder N-Cyclohexylmaleinimid; Allylverbindungen wie Allylbenzol und Allylester wie Allylacetat, Phthalsäurediallyl-ester, Isophthalsäurediallylester, Fumarsäurediallylester, Allyl-carbonate, Diallylcarbonate, Triallylphosphat und Triallylcy-45 anurat. 2S Suitable vinyl and vinylidene compounds copolymerizable with the unsaturated polyesters are suitable in polyester technology unsaturated compounds which preferably carry a-substituted vinyl groups or β-substituted allyl groups, preferably styrene; but also, for example, 30 nuclear chlorinated and alkylated or alkenylated styrenes, where the alkyl groups contain 1-4 carbon atoms, e.g. Vinyl toluene, divinylbenzene, a-methylstyrene, tert-butylstyrene, chlorostyrenes; Vinyl esters of carboxylic acids with 2-6 carbon atoms, preferably vinyl acetate; Vinyl pyridine, Vi-3S nylnaphthalene, vinylcyclohexane, acrylic acid and methacrylic acid and / or their esters (preferably vinyl, allyl and methallyl esters) with 1-4 carbon atoms in the alcohol component, their amides and nitriles, maleic anhydride, half and diesters with 1-4 carbon atoms in the alcohol component-40 te, half and diamides or cyclic imides such as N-methylma-linimide or N-cyclohexylmaleimide; Allyl compounds such as allylbenzene and allyl esters such as allyl acetate, diallyl phthalate, diallyl isophthalate, diallyl fumarate, allyl carbonates, diallyl carbonates, triallyl phosphate and triallylcy-45 anurate.
Die nachstehenden Beispiele erläutern die Erfindung. The following examples illustrate the invention.
Im folgenden angegebene Teile sind Gewichtsteile, Prozentangaben erfolgen als Gewichtsprozente. Parts given below are parts by weight, percentages are given as percentages by weight.
50 Beispiel 1 50 Example 1
In einem Lösungsmittelgemisch von 500 Teilen Toluol, 100 Teilen Phosphorsäuretris-(dimethylamid) und 50 Teilen Tetrahydrofuran werden 24 g Magnesium und 364 g Benzophenon vorgelegt. Bei einer Temperatur von 25-^-0 °C werden langsam 110 g Trichlormethylsilan zugetropft, wobei sich das Magnesium vollständig löst. Nach 4 Stunden Rühren bei 30 °C wird der Ansatz auf 11 Eis gegeben. Die organische Phase wird einige Male mit Wasser gewaschen und anschliessend bei 40 °C im Wasserstrahlvakuum eingeengt. Als Rückstand bleibt eine 60 hochviskose Flüssigkeit, die nach längerem Stehen zu einem glasartigen Festkörper erstarrt. 24 g of magnesium and 364 g of benzophenone are placed in a solvent mixture of 500 parts of toluene, 100 parts of phosphoric acid tris (dimethylamide) and 50 parts of tetrahydrofuran. At a temperature of 25 - ^ - 0 ° C, 110 g of trichloromethylsilane are slowly added dropwise, the magnesium dissolving completely. After 4 hours of stirring at 30 ° C., the mixture is poured onto 11 ice. The organic phase is washed a few times with water and then concentrated at 40 ° C. in a water jet vacuum. The residue is a 60 highly viscous liquid that solidifies into a glass-like solid after standing for a long time.
Die Gelchromatographie wurde mit einer niedermolekulartrennenden Säulenkombination, gefüllt mit «Styragel» verschiedener Porenweite (Waters-Messtechnik), durchgeführt; als Elu-ierungsmittel wurde Tetrahydrofuran eingesetzt. Die Eichung erfolgte mit Benzophenon, Acetophenon und Benzpinakol. Damit korreliert, ergibt sich folgende Molekulargewichtsverteilung. The gel chromatography was carried out with a column combination separating small molecules, filled with "Styragel" of different pore sizes (Waters measurement technique); tetrahydrofuran was used as the eluent. The calibration was carried out with benzophenone, acetophenone and benzpinacol. Correlated with this, the following molecular weight distribution results.
55 55
65 65
5 5
635 108 635 108
Komponente component
Molekulargewicht Molecular weight
Flächenprozent thylsilan in 200 ml abs. Tetrahydrofuran. Wenn das Natrium vollständig gelöst ist, wird noch 3 Stunden lang gerührt und der Area percent thylsilane in 200 ml abs. Tetrahydrofuran. When the sodium is completely dissolved, the mixture is stirred for a further 3 hours and the
1 1
182 182
1,4 1.4
Ansatz anschliessend mit 600 g Eis hydrolysiert. Nach mehrma The mixture is then hydrolyzed with 600 g of ice. After several years
2 2nd
366 366
5,2 5.2
ligem Waschen mit Eiswasser wird die organische Phase im washing with ice water, the organic phase in
3 3rd
520 520
2,3 2.3
5 Wasserstrahlvakuum bei 20 °C eingelegt. 5 Water jet vacuum inserted at 20 ° C.
4 4th
940 940
8,4 8.4
Gelchromatographie: Gel chromatography:
5 5
1400 1400
31,0 31.0
6 6
1700 1700
29,0 29.0
Komponente Molekulargewicht Flächenprozent Component molecular weight area percent
7 7
2100 2100
15,7 15.7
1 450 0,8 1 450 0.8
8 8th
2460 2460
6,8 6.8
io2 470 5,0 3 1000 33,5 io2 470 5.0 3 1000 33.5
Mn (osmometrisch): 1400 Mn (osmometric): 1400
4 1450 25,4 4 1450 25.4
5 1900 24,1 5 1900 24.1
Beispiel 2 Example 2
6 2700 11,0 6 2700 11.0
Beispiel 1 wird modifiziert: Anstelle des Benzophenons werden 240 g Acetophenon eingesetzt. Nach der Aufarbeitung bleibt ein festes Harz zurück. Example 1 is modified: Instead of the benzophenone, 240 g of acetophenone are used. After processing, a solid resin remains.
Gelchromatographie: Gel chromatography:
Komponente Molekulargewicht Flächenprozent Component molecular weight area percent
120 242 700 980 1800 2400 3600 120 242 700 980 1800 2400 3600
2,5 1,9 7,5 28,7 38,0 13,2 8,2 2.5 1.9 7.5 28.7 38.0 13.2 8.2
Beispiel 3 Example 3
In einem Lösungsmittelgemisch von 250 ml abs. Tetrahydrofuran und 50 ml Triäthylphosphat werden 23 g Natrium in Fäden eingepresst. Bei — 5 bis 10 °C tropft man dazu eine Lösung von 196 g 2-Methylbenzophenon und 66 g Dichlordime- In a solvent mixture of 250 ml abs. Tetrahydrofuran and 50 ml triethyl phosphate, 23 g sodium are pressed into threads. A solution of 196 g of 2-methylbenzophenone and 66 g of dichlorodime is added dropwise at -5 to 10 ° C.
Versuch A Trial A
Ein ungesättigter Polyester, hergestellt aus 11 Teilen Phthalsäureanhydrid, 47 Teilen Maleinsäureanhydrid und 42 Teilen Propylenglykol-1,2 bei 200 °C (Säurezahl 20, OH-Zahl 20 30, Viskosität bei 20 °C: 1500 mPa • s, wird 66%ig in Styrol gelöst, mit 0,01 Teil Hydrochinon stabilisiert und mit jeweils 0,3 Teilen der vorstehend angeführten Initiatoren 2,4, 8, 9,14,-16, 17 oder Benzpinakol abgemischt. Eine Stunde nach der Zugabe des Initiators werden 20 g eines Harzansatzes in ein Reagenz-25 glas von 16 mm Durchmesser gefüllt. Ein Eisen-Konstantan-Thermoelement, das mit einem Temperatur-Zeit-Schreiber verbunden ist, wird 3 cm tief in das Harz eingetaucht und das zu 8 cm gefüllte Reagenzglas nach dem Einschalten des Messgerätes in ein thermostatisiertes Ölbad gestellt. Analog DIN 16 945 30 werden die Härtungszeiten tH (Zeit bis zum Erreichen der Spitzentemperatur minus Zeit bis zum Überschreiten der 65 °C-Linie) und die Spitzentemperatur (Tm) bestimmt. An unsaturated polyester, made from 11 parts of phthalic anhydride, 47 parts of maleic anhydride and 42 parts of 1,2-propylene glycol at 200 ° C (acid number 20, OH number 20 30, viscosity at 20 ° C: 1500 mPa • s, is 66% dissolved in styrene, stabilized with 0.01 part of hydroquinone and mixed with 0.3 part of each of the above-mentioned initiators 2,4, 8, 9,14, -16, 17 or benzpinacol One hour after the addition of the initiator, 20 g of a resin batch is filled into a test tube of 16 mm diameter An iron constantan thermocouple, which is connected to a temperature-time recorder, is dipped 3 cm deep into the resin and the test tube filled to 8 cm after switching on of the measuring device in a thermostatted oil bath The hardening times tH (time to reach the peak temperature minus time to exceed the 65 ° C line) and the peak temperature (Tm) are determined in accordance with DIN 16 945 30.
Bei den angegebenen Badtemperaturen ergeben sich folgende Werte: The following values result at the specified bath temperatures:
2 2nd
4 4th
8 8th
9 9
14 14
16 16
17 17th
Benzpinakol Benzpinacol
Initiator tH Initiator tH
T T
1 m tH 1 m th
T T
Am tH At tH
T T
Am tH At tH
T T
Am tH At tH
T T
A m tH A m tH
T T
x m x m
Tm Tm
T T
x m x m
Badtemp. Bath temp.
ra ra
70 70
14.4 14.4
160 160
80 80
14,0 14.0
190 190
13,0 13.0
190 190
12,2 12.2
175 175
9,9 9.9
195 195
90 90
9,0 9.0
220 220
8,6 8.6
225 225
8,0 8.0
190 190
6,5 6.5
210 210
100 100
8,8 8.8
215 215
5,0 5.0
250 250
4,9 4.9
>250 > 250
4,6 4.6
210 210
4,3 4.3
235 12,5 235 12.5
225 225
110 110
7,5 7.5
220 220
5,8 5.8
•235 • 235
3,7 3.7
>250 > 250
3,7 3.7
>250 > 250
3,2 3.2
235 235
3,2 3.2
250 7,5 250 7.5
240 240
120 120
9,0 9.0
230 230
5,0 5.0
240 240
4,3 4.3
250 250
2,8 2.8
>250 > 250
2,8 2.8
>250 > 250
2,7 2.7
>250 > 250
2,8 2.8
>250 4,5 > 250 4.5
250 250
130 130
6,3 6.3
245 245
3,8 3.8
250 250
3,3 3.3
>250 > 250
2,2 2.2
>250 > 250
2,2 2.2
>250 > 250
2,2 2.2
>250 > 250
2,4 2.4
>250 3,6 > 250 3.6
>250 > 250
140 140
5,0 5.0
250 250
3,2 3.2
>250 > 250
2,8 2.8
>250 > 250
1,9 1.9
>250 > 250
1,9 1.9
>250 > 250
1,9 1.9
>250 > 250
2,1 2.1
>250 3,2 > 250 3.2
>250 > 250
Versuch B Attempt B
Versuch A wird mit der Änderung wiederholt, dass die mit den Initiatoren 2,4,8,9 und 14 abgemischten Harzansätze vor der Härtung vier Tage lang bei 60 °C gelagert werden. Die anschliessend durchgeführten Messungen ergaben keine Veränderungen der Spitzentemperaturen und der Härtungszeiten. Experiment A is repeated with the change that the resin mixtures mixed with the initiators 2, 4, 8, 9 and 14 are stored at 60 ° C. for four days before curing. The measurements subsequently carried out showed no changes in the peak temperatures and the curing times.
Versuch C Attempt C
Ein ungesättigtes Polyesterharz, hergestellt aus 11 Teilen Phthalsäureanhydrid, 47 Teilen Maleinsäureanhydrid und 42 Teilen Propylenglykol-1,2 bei 200 °C (Säurezahl 20, OH-Zahl 30, Viskosität bei 20 °C: 1500 mPa • s), wird 66%ig in Styrol gelöst und mit 0,01 Teil Hydrochinon stabilisiert. An unsaturated polyester resin, made from 11 parts of phthalic anhydride, 47 parts of maleic anhydride and 42 parts of 1,2-propylene glycol at 200 ° C (acid number 20, OH number 30, viscosity at 20 ° C: 1500 mPa • s), is 66% dissolved in styrene and stabilized with 0.01 part of hydroquinone.
100 Teile dieses Harzes werden mit 100 Teilen Kreide, 4 Teilen Zinkstearat und jeweils mit den folgenden, vorstehend angeführten Initiatoren abgemischt: 100 parts of this resin are mixed with 100 parts of chalk, 4 parts of zinc stearate and in each case with the following initiators listed above:
Versuch a: b: Experiment a: b:
ss c: ss c:
d: d:
0,2 Teile 0,4 Teile 0,8 Teile 0,75 Teile 0.2 parts 0.4 parts 0.8 parts 0.75 parts
Initiator 9 Initiator 9 Initiator 9 Initiator 9 Initiator 9 Initiator 9
tert.-Butylperbenzoat tert-butyl perbenzoate
Die Harzansätze werden zuerst 5 Stunden lang bei 50 °C und dann 24 Stunden lang bei Zimmertemperatur eingedickt 60 und anschliessend in Proben à 7,5 g in einer Laborpresse bei 140 °C gehärtet. Die Härtungszeiten sowie die Reststyrolgehal-te der polymerisierten Blöcke werden bestimmt. The resin batches are first thickened at 50 ° C. for 5 hours and then at room temperature for 24 hours 60 and then hardened in samples of 7.5 g each in a laboratory press at 140 ° C. The curing times and the residual styrene content of the polymerized blocks are determined.
Versuch a b Attempt a b
Härtungszeit [min] Curing time [min]
1,41 1,25 1.41 1.25
Reststyrolgehalt [%] Residual styrene content [%]
0,8 0,3 0.8 0.3
635 108 635 108
6 6
Versuch Härtungszeit Reststyrolgehalt Versuch D Trial curing time residual styrene content Trial D
[min] [ %] Versuch A wird mit dem Unterschied wiederholt, dass als [min] [%] Experiment A is repeated with the difference that as
Initiator Gemische aus Benzoylperoxid und dem Initiator 9 eingesetzt werden. Initiator mixtures of benzoyl peroxide and initiator 9 are used.
c 1,15 0,2 s Die Härtungszeiten tH (min) und die Maximaltemperaturen d 1,40 0,4 Tm ( °C) werden bestimmt. c 1.15 0.2 s The curing times tH (min) and the maximum temperatures d 1.40 0.4 Tm (° C) are determined.
Initiatorgemisch Badtemperaturen Initiator mixture bath temperatures
Teile Parts
Teile 9 Parts 9
80 °C 80 ° C
90 °C 90 ° C
100 °C 100 ° C
110 110
°C ° C
Peroxid peroxide
tH tH
T T
A m tH A m tH
T T
1 m tH 1 m th
T T
1 m tH 1 m th
T T
xm xm
0,15 0.15
_ _
— -
10,5 10.5
225 225
5,5 5.5
250 250
3,4 3.4
>250 > 250
0,15 0.15
0,1 0.1
15 15
210 210
6,0 6.0
240 240
4,0 4.0
>250 > 250
2,8 2.8
>250 > 250
0,15 0.15
0,3 0.3
10 10th
215 215
5,1 5.1
240 240
3,2 3.2
>250 > 250
2,2 2.2
>250 > 250
0,25 0.25
15 15
210 210
7,5 7.5
235 235
4,5 4.5
>250 > 250
2,8 2.8
>250 > 250
0,25 0.25
0,1 0.1
13 13
215 215
4,8 4.8
245 245
3,5 3.5
>250 > 250
2,3 2.3
>250 > 250
0,25 0.25
0,3 0.3
9 9
225 225
4,0 4.0
>250 > 250
2,7 2.7
>250 > 250
1,9 1.9
>250 > 250
0,5 0.5
10 10th
220 220
4,8 4.8
245 245
3,2 3.2
>250 > 250
2,2 2.2
>250 > 250
0,5 0.5
0,1 0.1
8 8th
228 228
4,0 4.0
>250 > 250
2,7 2.7
>250 > 250
2,0 2.0
>250 > 250
0,5 0.5
0,3 0.3
7 7
235 235
3,5 3.5
>250 > 250
2,3 2.3
>250 > 250
1,8 1.8
>250 > 250
1,0 1.0
_ _
6 6
235 235
3,4 3.4
250 250
2,6 2.6
>250 > 250
1,6 1.6
>250 > 250
1,0 1.0
0,1 0.1
5 5
243 243
2,3 2.3
>250 > 250
1,9 1.9
>250 > 250
1,5 1.5
>250 > 250
Versuch E Tries
33,3 %ige Lösungen von Butylacrylat in Toluol werden jeweils mit 0,1 Teil der vorstehend angeführten Initiatoren 9,10 bzw. Benzpinakol versetzt und in mehreren Portionen zu je 30 g auf die angegebene Temperatur erhitzt. Nach bestimmten Zeiten werden Proben entnommen, die mit 1 ml einer 4%igen Lösung von Hydrochinon in Äthylacetat versetzt und dann in eine offene Schale gegossen werden. Die Lösungsmittel werden durch 16-stündiges Erhitzen auf 100 °C verdampft und die Restmonomeren durch Tempern des Rückstandes bei 160 °C im Vakuumtrockenschrank (267 mbar) entfernt. 33.3% solutions of butyl acrylate in toluene are each mixed with 0.1 part of the initiators 9.10 or benzpinacol mentioned above and heated to the specified temperature in several portions of 30 g each. After certain times, samples are taken, which are mixed with 1 ml of a 4% solution of hydroquinone in ethyl acetate and then poured into an open dish. The solvents are evaporated by heating at 100 ° C. for 16 hours and the residual monomers are removed by tempering the residue at 160 ° C. in a vacuum drying cabinet (267 mbar).
Die gravimetrische Bestimmung der Rückstände ergibt folgende Anteile an polymerisierter Substanz [% der Einwaage]: The gravimetric determination of the residues gives the following proportions of polymerized substance [% of the weight]:
Polymerisationstemperatur: 100 °C Polymerization temperature: 100 ° C
Initiator initiator
Polymerisationszeit [min] Polymerization time [min]
Versuch F Attempt F
100 Teile Styrol werden mit 0,2 Teilen eines Initiators abgemischt und in einem thermostatisierten Ölbad bei 80 °C bzw. 110 °C polymerisiert. Die Reaktion wird nach bestimmten Zei-35 ten durch Abkühlen der Lösung abgebrochen und das polymeri-sierte Styrol durch Verdünnung mit dem fünffachen Volumen Methanol ausgefällt. 100 parts of styrene are mixed with 0.2 part of an initiator and polymerized in a thermostated oil bath at 80 ° C or 110 ° C. The reaction is stopped after certain times by cooling the solution and the polymerized styrene is precipitated by dilution with five times the volume of methanol.
Nach 1 Stunde wird das Polymerisat abgesaugt, mehrfach mit Methanol gewaschen und anschliessend im Valcuumtro-4o ckenschrank über Nacht bei 60 °C getrocknet. After 1 hour, the polymer is filtered off with suction, washed several times with methanol and then dried in a vacuum oven at 60 ° C. overnight.
Folgende Menge an polymerisiertem Styrol werden erhalten (% Polystyrol). The following amount of polymerized styrene is obtained (% polystyrene).
Polymerisationstemperatur: 80 °C Polymerization temperature: 80 ° C
Initiator initiator
Polymerisationszeit [min] 30 60 120 240 Polymerization time [min] 30 60 120 240
15 15
30 30th
60 60
120 120
240 240
Initiator 9 Initiator 9
0,7 0.7
3,8 3.8
10,0 10.0
17,3 17.3
Benzpinakol Benzpinacol
0 0
16 16
41 41
51 51
87 87
so Initiator 10 so initiator 10
2,5 2.5
7,0 7.0
14,0 14.0
20,2 20.2
Initiator 9 Initiator 9
2 2nd
35 35
60 60
84 84
96 96
Benzpinakol Benzpinacol
- -
- -
0,2 0.2
0,4 0.4
Initiator 10 Initiator 10
4 4th
28 28
54 54
76 76
91 91
ohne Initiator without initiator
— -
— -
— -
Polymerisationstemperatur: 120 °C Initiator Polymerisationszeit [min] Polymerization temperature: 120 ° C initiator polymerization time [min]
Polymerisationstemperatur: 110 °C Polymerization temperature: 110 ° C
15 15
30 30th
60 60
120 120
240 240
Benzpinakol Benzpinacol
15 15
33 33
58 58
75 75
96 96
Initiator 9 Initiator 9
27 27th
48 48
72 72
84 84
99 99
Initiator 10 Initiator 10
24 24th
42 42
68 68
82 82
97 97
Polymerisationstemperatur: 140 °C Initiator Polymerisationszeit [min] Polymerization temperature: 140 ° C initiator polymerization time [min]
15 15
30 30th
60 60
120 120
240 240
Benzpinakol Benzpinacol
21 21st
38 38
59 59
77 77
97 97
Initiator 9 Initiator 9
31 31
60 60
96 96
98 98
99 99
Initiator 10 Initiator 10
30 30th
62 62
88 88
94 94
99 99
55 55
Initiator initiator
Initiator 4 60 Initiator 9 Initiator 10 Benzpinakol ohne Initiator Initiator 4 60 initiator 9 initiator 10 benzpinacol without initiator
Polymerisationszeit [min] Polymerization time [min]
10 15 20 30 10 15 20 30
0,3 1,4 3,4 9,6 0.3 1.4 3.4 9.6
8,5 14,7 24,3 37,8 8.5 14.7 24.3 37.8
8,8 15,0 22,8 34,5 8.8 15.0 22.8 34.5
0,9 2,8 8,9 24,8 0.9 2.8 8.9 24.8
- - - 0,3 - - - 0.3
65 Beispiel 4 65 Example 4
In einem Lösungsmittelgemisch von 500 Teilen Toluol, 100 Teilen Phosphorsäuretris-(dimethylamid) und 50 Teilen Tetrahydrofuran werden 24 g Magnesium und 364 g Benzophenon 24 g of magnesium and 364 g of benzophenone are added to a solvent mixture of 500 parts of toluene, 100 parts of phosphoric acid tris (dimethylamide) and 50 parts of tetrahydrofuran
7 7
635 108 635 108
vorgelegt. Bei einer Temperatur von 25^K) °C werden langsam 6 2220 16 submitted. At a temperature of 25 ^ K) ° C slowly 6 2220 16
95 g Tetrachlorsilan zugetropft, wobei sich das Magnesium voll- 7 3000 5 95 g of tetrachlorosilane were added dropwise, the magnesium fully 7 3000 5
ständig löst. Nach 4 Stunden Rühren bei 30 °C wird der Ansatz auf 11 Eis gegeben. Die organische Phase wird einige Male mit Beispiel 5 Wasser gewaschen und anschliessend bei 40 °C im Wasser- 5 Beispiel 4 wird wiederholt ; anstelle des Tetrachlorsilans Strahlvakuum eingeengt. Der Rückstand wird nach mehrfachem wird jedoch ein Siloxan folgender Struktur Extrahieren mit 50 °C heissem Isopropanol getrocknet und anschliessend IR-spektroskopisch und gelchromatographisch ana- CH3 CH3 lysiert. I I constantly solves. After 4 hours of stirring at 30 ° C., the mixture is poured onto 11 ice. The organic phase is washed several times with Example 5 water and then at 40 ° C. in water - 5 Example 4 is repeated; instead of the tetrachlorosilane jet vacuum is concentrated. After several times, the residue is extracted with a siloxane of the following structure, dried with isopropanol at 50 ° C. and then analyzed by IR spectroscopy and gel chromatography using CH3 CH3. I I
Die Gelchromatographie wurde mit einer niedermolekular ioCH3-Si(-0-S i-O-S i-Cl)3 The gel chromatography was carried out using a low molecular weight ioCH3-Si (-0-S i-O-S i-Cl) 3
trennenden Säulenkombination, gefüllt mit «Styragel» verschie- I I separating column combination, filled with "Styragel" various I I
dener Porenweite (Waters-Messtechnik), durchgeführt; als Elu- CH3 CH3 whose pore size (Waters measurement technology) carried out; as Elu- CH3 CH3
ierungsmittel wurde Tetrahydrofuran eingesetzt. Die Eichung eingesetzt. etting agent was used tetrahydrofuran. The calibration used.
erfolgte mit Benzophenon und Benzpinakol. Damit korreliert, Nach der Aufarbeitung bleibt ein niedrigviskoses Öl zurück, was done with benzophenone and benzpinacol. Correlates with this, after working up, a low-viscosity oil remains,
ergibt sich folgende Molekulargewichtsverteilung: is 420 cP bei 22 °C. the following molecular weight distribution results: is 420 cP at 22 ° C.
Komponente Molekular- Anteil [%] Molecular component [%]
gewicht Weight
1 ca. 350 15 (Benzpinakol) 1 approx. 350 15 (benzpinacol)
2 ca. 520 6 2 approx. 520 6
3 950 9 3 950 9
4 1350 22 4 1350 22
5 1800 27 5 1800 27
Versuch G Attempt G
Ein ungesättigter Polyester, hergestellt wie in Versuch A beschrieben, wird 66%ig in Styrol gelöst, mit 0,01 Teil Hydro-20 chinon stabilisiert und mit jeweils 0,3 Teilen der Initiatoren nach Beispielen 4 bzw. 5 bzw. mit Benzpinakol abgemischt. An unsaturated polyester, prepared as described in test A, is 66% dissolved in styrene, stabilized with 0.01 part of hydro-20 quinone and mixed with 0.3 part of the initiators according to Examples 4 and 5 or with benzpinacol.
Die Messungen erfolgen nach derselben Methode wie in Versuch A beschrieben. The measurements are carried out according to the same method as described in experiment A.
Bei den angegebenen Badtemperaturen ergeben sich fol-25 gende Werte: The following values result at the specified bath temperatures:
Initiator nach Beispiel 4 nach Beispiel 5 Benzpinakol Initiator according to example 4 according to example 5 benzpinacol
Badtemp. [ °C] tH [min] Tm [ °C] tH [min] Tm [ °C] tH [min] Tm [ °C] Bath temp. [° C] tH [min] Tm [° C] tH [min] Tm [° C] tH [min] Tm [° C]
110 110
6,5 6.5
250 250
5,6 5.6
240 240
7,5 7.5
240 240
120 120
3,6 3.6
250 250
3,9 3.9
250 250
4,5 4.5
250 250
130 130
2,6 2.6
250 250
3,0 3.0
250 250
3,6 3.6
250 250
140 140
2,1 2.1
250 250
2,4 2.4
250 250
3,2 3.2
250 250
C C.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19762632294 DE2632294C2 (en) | 1976-07-17 | 1976-07-17 | Silyl ethers and their use as polymerization initiators |
DE19762656782 DE2656782A1 (en) | 1976-12-15 | 1976-12-15 | oligomeric silyl ether, useful free radical initiator - for polymerisation of unsaturated monomer and polyester resin |
Publications (1)
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CH635108A5 true CH635108A5 (en) | 1983-03-15 |
Family
ID=25770714
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Application Number | Title | Priority Date | Filing Date |
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CH882577A CH635108A5 (en) | 1976-07-17 | 1977-07-15 | METHOD FOR PRODUCING REACTION MIXTURES THAT ARE SUITABLE AS INITIATORS FOR RADICALLY INITIATABLE POLYMERIZATION REACTIONS. |
Country Status (11)
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US (1) | US4145507A (en) |
JP (1) | JPS5312815A (en) |
AT (1) | AT370121B (en) |
CH (1) | CH635108A5 (en) |
DK (1) | DK321877A (en) |
ES (1) | ES460791A1 (en) |
FR (1) | FR2372189A1 (en) |
GB (1) | GB1584108A (en) |
IT (1) | IT1079787B (en) |
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SE (1) | SE435720B (en) |
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US4393185A (en) * | 1981-06-02 | 1983-07-12 | Ciba-Geigy Corporation | Thermally polymerizable mixtures and processes for the thermally-initiated polymerization of cationically polymerizable compounds |
US4544724A (en) * | 1984-06-19 | 1985-10-01 | E. I. Du Pont De Nemours And Company | Silylated vinyl alcohol polymers |
US4535174A (en) * | 1984-11-02 | 1985-08-13 | General Electric Company | Free-radical initiators and method for making |
IT1216719B (en) * | 1988-01-28 | 1990-03-08 | Milano | THERMODEGRADABLE COMPOSITIONS ABASE OF OMO OR CRYSTALLINE COPOLYMERS OF PROPYLENE AND PROCEDURE TO PERFORM THE SELECTIVE DEGRADATION OF SUCH OMO AND COPOLYMERS. |
NL8901728A (en) * | 1989-07-06 | 1991-02-01 | Stamicarbon | INITIATOR AND METHOD FOR CATIONIC POLYMERIZATION. |
US5665829A (en) * | 1990-02-08 | 1997-09-09 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Gt. Britain & Northern Ireland | Process for the polymerization of olefinic-containing monomers employing anionic initiators |
GB9002804D0 (en) * | 1990-02-08 | 1990-04-04 | Secr Defence | Anionic polymerisation |
DE19611452A1 (en) * | 1995-03-27 | 1996-10-02 | Shinetsu Chemical Co | Waterproofing absorbent construction materials |
CN113518805B (en) * | 2018-12-28 | 2023-08-08 | 意大利艾坚蒙树脂有限公司 | Photoinitiator |
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US2559342A (en) * | 1949-07-26 | 1951-07-03 | Gen Electric | Organo-silicon compositions |
BE554172A (en) * | 1956-01-18 | |||
US3078184A (en) * | 1960-09-23 | 1963-02-19 | Union Carbide Corp | Disilatrioxanes, process for preparing same, process for coating metal, and coated metal |
US3287291A (en) * | 1962-07-12 | 1966-11-22 | Union Carbide Corp | Diorganosiloxanes cured with an alkoxy end-blocked silyl tetraformal |
CH591535A5 (en) * | 1974-03-25 | 1977-09-30 | Ciba Geigy Ag |
-
1977
- 1977-07-08 NL NLAANVRAGE7707635,A patent/NL168232C/en not_active IP Right Cessation
- 1977-07-13 US US05/815,159 patent/US4145507A/en not_active Expired - Lifetime
- 1977-07-13 GB GB29443/77A patent/GB1584108A/en not_active Expired
- 1977-07-13 FR FR7721790A patent/FR2372189A1/en active Granted
- 1977-07-14 SE SE7708183A patent/SE435720B/en not_active IP Right Cessation
- 1977-07-15 CH CH882577A patent/CH635108A5/en not_active IP Right Cessation
- 1977-07-15 DK DK321877A patent/DK321877A/en unknown
- 1977-07-15 ES ES460791A patent/ES460791A1/en not_active Expired
- 1977-07-15 JP JP8432677A patent/JPS5312815A/en active Granted
- 1977-07-15 IT IT50309/77A patent/IT1079787B/en active
- 1977-07-15 AT AT0513677A patent/AT370121B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
SE435720B (en) | 1984-10-15 |
DK321877A (en) | 1978-01-18 |
GB1584108A (en) | 1981-02-04 |
ES460791A1 (en) | 1978-12-01 |
NL168232C (en) | 1982-03-16 |
JPS5312815A (en) | 1978-02-04 |
JPS6152836B2 (en) | 1986-11-14 |
NL7707635A (en) | 1978-01-19 |
FR2372189B1 (en) | 1984-03-16 |
ATA513677A (en) | 1982-07-15 |
FR2372189A1 (en) | 1978-06-23 |
IT1079787B (en) | 1985-05-13 |
NL168232B (en) | 1981-10-16 |
AT370121B (en) | 1983-03-10 |
US4145507A (en) | 1979-03-20 |
SE7708183L (en) | 1978-01-18 |
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Legal Events
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PL | Patent ceased |